EP0205613B1 - Procede de formation des couches de bioxyde de silicium nitrure pour circuits integres a semiconducteurs - Google Patents
Procede de formation des couches de bioxyde de silicium nitrure pour circuits integres a semiconducteurs Download PDFInfo
- Publication number
- EP0205613B1 EP0205613B1 EP86901000A EP86901000A EP0205613B1 EP 0205613 B1 EP0205613 B1 EP 0205613B1 EP 86901000 A EP86901000 A EP 86901000A EP 86901000 A EP86901000 A EP 86901000A EP 0205613 B1 EP0205613 B1 EP 0205613B1
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- European Patent Office
- Prior art keywords
- layer
- silicon dioxide
- top surface
- nitrided
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 38
- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 238000004151 rapid thermal annealing Methods 0.000 claims description 9
- 238000005121 nitriding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 3
- -1 silicon nitroxide Chemical class 0.000 abstract description 31
- 150000001875 compounds Chemical class 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 9
- 229910021332 silicide Inorganic materials 0.000 description 9
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/022—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02329—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen
- H01L21/02332—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen into an oxide layer, e.g. changing SiO to SiON
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
- H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
Definitions
- This invention relates to semiconductor devices and more particularly to silicon-integrated circuits which comprise silicon dioxide layers.
- Semiconductor integrated circuits comprise a multiplicity of transistor devices integrated at a major surface of a semiconductor medium, typically a monocrystalline silicon or gallium arsenide semiconductor chip. Silicon dioxide layers are useful in these integrated circuits for serving such purposes as gate oxide dielectric layers of MOS (metal oxide semiconductor) transistors and as passivation oxide dielectric layers located on the major surface of the semiconductor between transistors (whether MOS or not) for mutually electrically isolating the transistors.
- MOS metal oxide semiconductor
- the lateral size of each transistor is made as small as possible in order to fit as many transistors as possible on the major surface of a single semiconductor chip and to enhance the speed of circuit operation.
- the thickness of the silicon dioxide gate dielectric ("gate oxide") layer separating the gate electrode of an MOS transistor from the underlying major surface of the semiconductor body ideally should be made correspondingly (but not necessarily linearly) smaller.
- the thickness of the gate oxide is thus made smaller than about 20 nm (200 Angstroms); however, impurities from the overlying gate electrode can then undesirably penetrate through the gate oxide to the interface of the oxide with the underlying semiconductor and thereby cause undesirable transistor threshold voltage shifts.
- silicon nitroxide (oxynitride) layer overlying a silicon dioxide layer as a gate oxide of an MOS transistor can act as an effective barrier (or seal) against the undesirable penetration through the gate oxide by many impurities-such as boron, oxygen, nitrogen, sodium, arsenic, and phosphorus (but not water). It is also known in the art that silicon nitroxide layers that contain nitrogen in an amount corresponding to a nitrogen atomic concentration fraction [N/(N+O)] (simply called “nitrogen fraction” hereafter) in the approximate range of 0.10 to 0.20, especially approximately 0.12 to 0.14, are extremely effective barriers against both oxygen and silicon diffusion.
- nitrogen fraction nitrogen fraction
- silicon nitride layer decomposes rapidly at high temperatures in an oxygen ambient.
- the product of this decomposition is a silicon nitroxide layer whose composition ranges from almost pure oxide to almost pure nitride; therefore, in particular, a region of this layer has a nitrogen atomic fraction of about 0.12 to 0.14, and it is this region that is believed to be responsible for the effective barrier posed by the "silicon nitride" layer (compound layer of silicon nitroxide on silicon nitride) against the diffusion of oxygen.
- a silicon nitroxide layer as a barrier layer for such purposes as sealing the gate oxide of an MOS transistor against undesirable diffusants.
- Such sealing in the case of an n-channel MOS transistor is needed in particular for protecting the oxide- semiconductor interface against the diffusion of arsenic or phosphorus (which is ordinarily used to dope the polysilicon gate electrode) from the gate electrode through the gate oxide; in the case of a p-channel transistor, against the diffusion of boron.
- Prior art techniques for thus sealing a thin gate oxide layer include forming such a silicon nitroxide layer at the top of the oxide layer, as by nitriding a silicon dioxide layer by heating it in ammonia gas.
- the impurity regions in the semiconductor are undesirably affected not only by undesirable changes of impurity concentrations therein but also by undesirable movements of the junction profiles that define the boundaries between contiguous regions of opposite (p and n) conductivity types or of the same types but differing conductivity magnitudes.
- the problem due to the formation of trapping centres is solved by a process as set out in claim 1.
- the claimed process also solves the problem of prolonged high temperature treatments.
- Figs. 1-5 depict an illustrative cross section of a portion of an integrated circuit including an MOS transistor, during various successive manufacturing stages of the circuit in accordance with one embodiment of this invention.
- the nitrided layer can be formed by nitriding a top portion of a silicon dioxide layer located on an underlying semiconductor medium-such nitriding being performed by means of a rapid thermal annealing of the silicon dioxide layer to an elevated temperature, of about 1200 to 1250 degrees C or more, in an ambient containing nitrogen, preferably pure ammonia.
- rapidly thermal annealing it is meant that the layer is heated from an initial relatively low temperature (such as room temperature) within a first relatively short time interval t 1 to the elevated temperature, is then maintained at this elevated temperature (at least approximately or somewhat higher) for a second relatively short time interval t 2 , and immediately thereafter is cooled to a final relatively low temperature (as by radiation to the room) within a third relatively short time interval t 3 .
- relatively low temperature it is meant any temperature which is sufficiently low, typically about 500 degrees C or less, so that diffusion of nitrogen or other significant impurity is unimportant either in the oxide or in the underlying semiconductor (if any).
- the initial and final relatively low temperature may or may not be the same.
- the time intervals t 1 , t 2 and t 3 are all about ten seconds or less but can usefully be as long as about a minute or two.
- a desirable barrier layer of silicon nitroxide having a nitrogen fraction above about 0.13 At a top portion of the thus nitrided silicon dioxide layer there is formed a desirable barrier layer of silicon nitroxide having a nitrogen fraction above about 0.13.
- the nitrogen profile in the nitrided layer is further characterized in that the nitrogen fraction falls from a value above 0.13 (typically about 0.35) at the top surface of the layer to a value of about 0.13 within a first distance d which, on the basis of Auger measurement, is believed to be about 1.5 to 2.5 nm (15 to 25 Angstroms), and is assuredly less than about 3 nm (30 Angstroms), as measured from this top surface of the layer.
- this nitrogen fraction falls to a value below about 0.05 at a distance d 2 equal to or less than 6 nm (60 Angstroms) from the top surface of the thus nitrided silicon dioxide layer, and advantageously the nitrogen fraction also stays less than this value of about 0.05 in the layer all the way down to a third distance x of about 2 nm (20 Angstroms) or less from the interface with the underlying semiconductor medium.
- the sum of the second distance d 2 and the third distance x is less than the thickness of the nitrided silicon dioxide layer (in order for there to be a remaining intermediate region).
- the relatively low value of about 0.05 for the nitrogen fraction in the intermediate region prevents undesirable segregation of nitrogen toward the underlying semiconductor medium.
- the nitrided silicon dioxide layer everywhere at all distances greater than the second distance d 2 from the top surface is thus advantageously free of any significant amounts of nitrogen whether or not it is bonded to other atoms.
- the rapid thermal annealing time or temperature (or both) is adjusted so that the nitrogen fraction that results at the top surface of the nitrided oxide layer is greater than about 0.13.
- the distance d can thus be viewed as the (effective) thickness d of a silicon nitroxide portion of a compound layer consisting of a silicon nitroxide portion on a silicon dioxide portion, or as the (effective) thickness of a silicon nitroxide layer located on a silicon dioxide layer.
- This thickness d of the silicon nitroxide layer when formed by sufficiently rapid thermal annealing at sufficiently high temperature (in particular, about 1200 degrees C), tends to be self-limited to about 3 nm (30 Angstroms) or less. It is theorized that this self-limiting occurs because the silicon nitroxide layer formed by sufficiently rapid thermal annealing at sufficiently high temperatures acts as an effective barrier against further diffusion of nitrogen deeper into the underlying silicon dioxide as soon as thickness of nitroxide is formed, that is, before significant amounts of nitrogen have had a chance to diffuse deeper into the silicon dioxide.
- sufficiently high temperature in particular, about 1200 degrees C
- this relatively small thickness d of the silicon nitroxide is theorized to be small enough to enable direct tunneling from an overlying metal layer, such as a gate electrode in a MOS transistor, directly contacting the top surface of the silicon nitroxide to any trapping centers that are located in the silicon nitroxide within this distance d, whereby undesirable charging of the trapping centers will be desirably discharged.
- the remaining silicon dioxide layer (underlying the silicon nitroxide layer) is relatively free of nitrogen.
- this invention involves a compound layer consisting essentially of a silicon nitroxide portion on a silicon dioxide portion in which the nitrogen fraction falls from a value greater than 0.13 at the top surface of the compound layer to a value of about 0.13 at a first distance d of about 3 nm (30 Angstroms) (or less) and to a value of about 0.05 (or less) at a second distance d 2 as measured from this top surface, and stays below this value of about 0.05 throughout the remainder of the way down from this distance d 2 to a distance x of about 2 nm (20 Angstroms) or less from the bottom surface of the compound layer, and the nitrogen fraction in the layer is less than about 0.15 everywhere within the distance x from the bottom surface of the compound layer.
- the compound layer of silicon nitroxide on silicon dioxide can be used to seal an underlying medium, such as a nitrogen, sodium, arsenic, and phosphorus.
- An MOS capacitor having as a dielectric a compound layer of silicon nitroxide on silicon dioxide in accordance with the invention, has been successfully built and tested as to its capacitance-voltage profile over a voltage range of about 5 volts of both polarities, thereby demonstrating an absence of undesirable charge trapping phenomena.
- an MOS transistor in an integrated circuit has a compound layer of silicon nitroxide on silicon dioxide having a thickness in the approximate range of 5 to 40 nm (50 to 400 Angstroms) separating an overlying gate electrode from an underlying major surface of a semiconductor medium in which the circuit is integrated.
- the gate electrode is composed of a metal-like (metal silicide) layer directly contacting the top surface of the nitroxide layer.
- nitrided silicon dioxide layer overlies a semiconductor medium at areas between transistors integrated therein, so that the layer can serve as passivation dielectric for electrically isolating the transistors from one another and at the same time preventing undesired impurities from entering the semiconductor from the ambient.
- a top major surface 10.5 of a p-type monocrystalline silicon semiconductor medium 10 is coated with a relatively thick field oxide layer 12, which has been thermally grown by conventional means to a uniform thickness of typically about 300 nm (3,000 Angstroms), and a relatively thin gate oxide layer 11, which has been thermally grown by conventional means to a uniform thickness of about 10 nm (100 Angstroms).
- This field oxide thickness can usefully also be in the approximate range of 200-500 nm (2,000 to 5,000 Angstroms); and this gate oxide thickness, in the approximate range of 5 to 20 nm (50 to 200 Angstroms).
- the top portions of the field oxide and gate oxide layers are nitrided to form a silicon nitroxide layer 22.
- a relatively thin composite dielectric layer consisting essentially of a silicon nitroxide portion 22 on the remaining silicon dioxide portion 21 having the above prescribed nitrogen fraction profile.
- the nitrogen fraction at the top surface 22.5 of the nitroxide portion 22 is about 0.35, and it falls to about 0.13 at a distance in the range of about 1.5 to 2.5 nm (15 to 25 Angstroms) beneath this top surface 22.5 of the layer 22, and to less than 0.05 everywhere at distances of greater than about 6 nm (60 Angstroms) beneath this top surface 22.5.
- the structure shown in Fig. 1 is initially at room temperature and is placed in an RTA (rapid thermal annealing) chamber of a heating apparatus, for example, of the kind described in a paper entitled “Recrystallization of Polysilicon Films Using Incoherent Light", authored by A. Kamgar and E. Labate, published in Materials Letters, Vol. 1, No. 3, 4, at pp. 91-94 (December 1982).
- the chamber in which the structure is placed is subjected to flow of commercially available ultra-high pure ammonia at a flow rate of one cm/sec at essentially atmospheric pressure.
- the power delivered to the tungsten lamps which act as the heating source for the rapid thermal annealing is adjusted so that the temperature (as measured by a pyrometer) of the structure goes from room temperature to an elevated temperature of about 1250 degrees C (or more) within about 10 seconds and remains at 1250 degrees C (or somewhat still more, such as up to about 1300 degrees C) for another 10 seconds.
- the power to the tungsten lamps is shut off, and thereby the structure cools to about 500 degrees C within yet another 10 seconds.
- the elevated temperature was measured as 1250 degrees C, there is a possible error of as much as 50 degrees, so that the elevated temperature may actually have been as low as 1200 degrees C or as high as 1300 degrees C. Moreover, the elevated temperature as thus measured may be made to be as high as 1300 degrees C or more during the heating in which case the time during which the temperature of the structure is made to remain at the elevated temperature is correspondingly reduced to less than 10 seconds.
- a TEOS (tetra ethyl ortho silicate) layer 24 typically about 250 nm (2,500 Angstroms) thick, is deposited by conventional means.
- the structure is anisotropically etched, as by reactive ion etching with ions, whereby the top surface of the polysilicon layer 23 and portions of the top major surface 10.5 of the semiconductor are laid bare.
- a silicon dioxide portion 31 and a silicon nitroxide portion 32 both stemming from the thin oxide layer 21 and 22, respectively
- another silicon dioxide portion 41 and another silicon nitroxide portion 42 also both stemming from the layers 21 and 22
- a TEOS sidewall portion 34 remains on the sidewall of the polysilicon layer 23
- another TEOS portion 44 remains on the silicon nitroxide portion 42.
- a silicide forming metal such as cobalt or titanium, is deposited to a thickness of typically about 150 nm (1,500 Angstroms) and is sintered to form metal silicide in those regions thereof overlying silicon, and is wet etched with an etching solution, such as aqua regia, which removes the metal but not the metal silicide or the oxides (including TEOS).
- an etching solution such as aqua regia, which removes the metal but not the metal silicide or the oxides (including TEOS).
- the structure is then subjected to a phosphorus diffusion step, whereby the phosphorus diffuses into metal silicide gate electrode 53, as well as through the metal silicide gate source and drain electrodes into the underlying silicon semiconductor to form n+ regions that are aligned with the edges of the gate electrode 53 as understood in the art.
- an undoped glass layer 51 is deposited, to a thickness of typically about 500 nm (5,000 Angstroms), and patterned with windows to enable electrical access to the source and drain electrodes.
- the gate electrode layer 53 ordinarily extends in a direction perpendicular to the plane of Fig. 5 to a region overlying field oxide where the undoped glass layer 51 also extends and can be provided with a window for access to the gate electrode.
- an aluminum layer is deposited and patterned (as well as further interconnections, as known in the art) to form access metallizations 54 and 55 for the source and drain electrodes 56 and 57 in accordance with the desired integrated circuit interconnections.
Abstract
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US678569 | 1984-12-05 | ||
US06/678,569 US4623912A (en) | 1984-12-05 | 1984-12-05 | Nitrided silicon dioxide layers for semiconductor integrated circuits |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0205613A1 EP0205613A1 (fr) | 1986-12-30 |
EP0205613B1 true EP0205613B1 (fr) | 1990-07-11 |
Family
ID=24723349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86901000A Expired - Lifetime EP0205613B1 (fr) | 1984-12-05 | 1985-11-13 | Procede de formation des couches de bioxyde de silicium nitrure pour circuits integres a semiconducteurs |
Country Status (9)
Country | Link |
---|---|
US (1) | US4623912A (fr) |
EP (1) | EP0205613B1 (fr) |
JP (1) | JP2568527B2 (fr) |
KR (1) | KR960000378B1 (fr) |
CA (1) | CA1260364A (fr) |
DE (1) | DE3578656D1 (fr) |
ES (1) | ES8801968A1 (fr) |
IE (1) | IE57207B1 (fr) |
WO (1) | WO1986003621A1 (fr) |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4882649A (en) * | 1988-03-29 | 1989-11-21 | Texas Instruments Incorporated | Nitride/oxide/nitride capacitor dielectric |
JPH0793298B2 (ja) * | 1988-10-11 | 1995-10-09 | 日本電気株式会社 | 半導体装置の形成方法 |
US5874766A (en) * | 1988-12-20 | 1999-02-23 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device having an oxynitride film |
JPH02288235A (ja) * | 1989-04-27 | 1990-11-28 | Fujitsu Ltd | 半導設装置の製造方法 |
US5242848A (en) * | 1990-01-22 | 1993-09-07 | Silicon Storage Technology, Inc. | Self-aligned method of making a split gate single transistor non-volatile electrically alterable semiconductor memory device |
US5572054A (en) * | 1990-01-22 | 1996-11-05 | Silicon Storage Technology, Inc. | Method of operating a single transistor non-volatile electrically alterable semiconductor memory device |
JP2907344B2 (ja) * | 1990-06-27 | 1999-06-21 | 株式会社東芝 | 半導体装置およびその製造方法 |
US5254489A (en) * | 1990-10-18 | 1993-10-19 | Nec Corporation | Method of manufacturing semiconductor device by forming first and second oxide films by use of nitridation |
KR940011483B1 (ko) * | 1990-11-28 | 1994-12-19 | 가부시끼가이샤 도시바 | 반도체 디바이스를 제조하기 위한 방법 및 이 방법에 의해 제조되는 반도체 디바이스 |
JP2652108B2 (ja) * | 1991-09-05 | 1997-09-10 | 三菱電機株式会社 | 電界効果トランジスタおよびその製造方法 |
US5250456A (en) * | 1991-09-13 | 1993-10-05 | Sgs-Thomson Microelectronics, Inc. | Method of forming an integrated circuit capacitor dielectric and a capacitor formed thereby |
US5449941A (en) * | 1991-10-29 | 1995-09-12 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor memory device |
US5726087A (en) * | 1992-04-30 | 1998-03-10 | Motorola, Inc. | Method of formation of semiconductor gate dielectric |
US5392189A (en) | 1993-04-02 | 1995-02-21 | Micron Semiconductor, Inc. | Capacitor compatible with high dielectric constant materials having two independent insulative layers and the method for forming same |
US6531730B2 (en) | 1993-08-10 | 2003-03-11 | Micron Technology, Inc. | Capacitor compatible with high dielectric constant materials having a low contact resistance layer and the method for forming same |
US6791131B1 (en) * | 1993-04-02 | 2004-09-14 | Micron Technology, Inc. | Method for forming a storage cell capacitor compatible with high dielectric constant materials |
TW264575B (fr) | 1993-10-29 | 1995-12-01 | Handotai Energy Kenkyusho Kk | |
US5397720A (en) * | 1994-01-07 | 1995-03-14 | The Regents Of The University Of Texas System | Method of making MOS transistor having improved oxynitride dielectric |
US5629221A (en) * | 1995-11-24 | 1997-05-13 | National Science Council Of Republic Of China | Process for suppressing boron penetration in BF2 + -implanted P+ -poly-Si gate using inductively-coupled nitrogen plasma |
US5808335A (en) * | 1996-06-13 | 1998-09-15 | Vanguard International Semiconductor Corporation | Reduced mask DRAM process |
US5969397A (en) * | 1996-11-26 | 1999-10-19 | Texas Instruments Incorporated | Low defect density composite dielectric |
US6331468B1 (en) * | 1998-05-11 | 2001-12-18 | Lsi Logic Corporation | Formation of integrated circuit structure using one or more silicon layers for implantation and out-diffusion in formation of defect-free source/drain regions and also for subsequent formation of silicon nitride spacers |
US6177363B1 (en) | 1998-09-29 | 2001-01-23 | Lucent Technologies Inc. | Method for forming a nitride layer suitable for use in advanced gate dielectric materials |
US6380055B2 (en) | 1998-10-22 | 2002-04-30 | Advanced Micro Devices, Inc. | Dopant diffusion-retarding barrier region formed within polysilicon gate layer |
US6087236A (en) * | 1998-11-24 | 2000-07-11 | Intel Corporation | Integrated circuit with multiple gate dielectric structures |
US6303520B1 (en) | 1998-12-15 | 2001-10-16 | Mattson Technology, Inc. | Silicon oxynitride film |
JP3350478B2 (ja) * | 1999-04-21 | 2002-11-25 | 宮城沖電気株式会社 | 半導体素子の製造方法 |
US6323143B1 (en) * | 2000-03-24 | 2001-11-27 | Taiwan Semiconductor Manufacturing Company | Method for making silicon nitride-oxide ultra-thin gate insulating layers for submicrometer field effect transistors |
US6559007B1 (en) * | 2000-04-06 | 2003-05-06 | Micron Technology, Inc. | Method for forming flash memory device having a tunnel dielectric comprising nitrided oxide |
ATE267620T1 (de) | 2000-08-28 | 2004-06-15 | Medela Ag | Brusthaubeneinsatz |
US6544908B1 (en) * | 2000-08-30 | 2003-04-08 | Micron Technology, Inc. | Ammonia gas passivation on nitride encapsulated devices |
WO2003015181A1 (fr) * | 2001-08-10 | 2003-02-20 | Spinnaker Semiconductor, Inc. | Transistor a couche isolante de porte a constante dielectrique elevee et source et drain formant un contact schottky avec le substrat |
US6878415B2 (en) * | 2002-04-15 | 2005-04-12 | Varian Semiconductor Equipment Associates, Inc. | Methods for chemical formation of thin film layers using short-time thermal processes |
US6780720B2 (en) | 2002-07-01 | 2004-08-24 | International Business Machines Corporation | Method for fabricating a nitrided silicon-oxide gate dielectric |
KR20110057645A (ko) * | 2009-11-24 | 2011-06-01 | 삼성전자주식회사 | 절연막 형성 방법 및 이를 포함하는 트랜지스터 형성 방법 |
KR101562020B1 (ko) * | 2010-02-22 | 2015-10-21 | 삼성전자주식회사 | 반도체 소자 및 그 제조 방법 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0072603B1 (fr) * | 1978-06-14 | 1986-10-01 | Fujitsu Limited | Procédé de fabrication d'un dispositif semiconducteur muni d'une couche isolante de dioxyde de silicium couverte d'une couche d'oxynitrure de silicium |
-
1984
- 1984-12-05 US US06/678,569 patent/US4623912A/en not_active Expired - Lifetime
-
1985
- 1985-11-13 DE DE8686901000T patent/DE3578656D1/de not_active Expired - Fee Related
- 1985-11-13 WO PCT/US1985/002243 patent/WO1986003621A1/fr active IP Right Grant
- 1985-11-13 KR KR1019860700526A patent/KR960000378B1/ko not_active IP Right Cessation
- 1985-11-13 EP EP86901000A patent/EP0205613B1/fr not_active Expired - Lifetime
- 1985-11-13 JP JP61501072A patent/JP2568527B2/ja not_active Expired - Fee Related
- 1985-11-28 CA CA000496463A patent/CA1260364A/fr not_active Expired
- 1985-12-04 IE IE3050/85A patent/IE57207B1/en not_active IP Right Cessation
- 1985-12-04 ES ES549560A patent/ES8801968A1/es not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1260364A (fr) | 1989-09-26 |
JP2568527B2 (ja) | 1997-01-08 |
DE3578656D1 (de) | 1990-08-16 |
EP0205613A1 (fr) | 1986-12-30 |
ES8801968A1 (es) | 1988-03-16 |
KR880700460A (ko) | 1988-03-15 |
KR960000378B1 (ko) | 1996-01-05 |
JPS62501184A (ja) | 1987-05-07 |
ES549560A0 (es) | 1988-03-16 |
US4623912A (en) | 1986-11-18 |
IE57207B1 (en) | 1992-06-03 |
IE853050L (en) | 1986-06-05 |
WO1986003621A1 (fr) | 1986-06-19 |
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